The present invention relates to filter materials. More particularly, the present invention relates to charge-modified filters.
Charge-modified filters are known in the art. They typically consist of microporous membranes or involve the use of materials which are blends of glass fibers and cellulose fibers or blends of cellulose fibers and siliceous particles. Charge modification generally was accomplished by coating the membrane or at least some of the fibers with a charge-modifying agent and a separate crosslinking agent in order to ensure the durability of the coating.
While microporous membranes generally are capable of effective filtration, flow rates through the membrane typically are lower than for fibrous filters. Moreover, microporous membranes also generally have higher back pressures during the filtration process than do fibrous filters. Accordingly, there is a need for fibrous filters having effective filtration capabilities for charged particles. Moreover, there also is a need for fibrous filters composed of glass fibers, without the need for cellulosic fibers or siliceous particles.
Apertured films, woven fabrics and nonwoven materials have been used as filter sheets for removing or separating particles from liquids. Such filter sheets generally rely on some form of mechanical straining or physical entrapment. Such filter sheets can pose limitations when the size of the particle to be removed is small relative to the average pore diameter of the filter sheet. For nonwoven materials, this is particularly true for particles of less than one micrometer in diameter.
Improved filters have been developed with modified surface charge characteristics to capture and adsorb particles by electrokinetic interaction between the filter surface and particles contained in an aqueous liquid. Such charge-modified filters typically consist of microporous membranes or involve the use of materials which are blends of glass fibers and cellulose fibers or blends of cellulose fibers and siliceous particles. Charge modification generally was accomplished by coating the membrane or at least some of the fibers with a charge-modifying agent and a separate crosslinking agent in order to ensure the durability of the coating.
While microporous membranes generally are capable of effective filtration, flow rates through the membrane typically are lower than for fibrous filters. Moreover, microporous membranes also generally have higher back pressures during the filtration process than do fibrous filters.
The use of fibers prepared from synthetic polymers is desirable because such fibers are inexpensive and they can be formed into nonwoven webs having porosities which are appropriate for the filtration of particles from a fluid stream. Many of such synthetic polymers, however, are hydrophobic, a characteristic which makes it difficult to durably coat fibers prepared from such polymers with a charge-modifying material. Accordingly, opportunities exist for improved charge-modified filter materials which are based on hydrophobic polymer fibers.
Stated differently, it would be desirable if certain inexpensive materials could be used to produce filters having modified surface charge characteristics for filtering very fine particles from aqueous liquids. For example, polyolefins are widely used in the manufacture of sheets of apertured films, woven fabrics, and nonwoven materials. Many types of polyolefin sheets tend to be hydrophobic and relatively inert. That is, the low surface free energy of polyolefins (e.g., polypropylene) and their relatively chemically inert natures render many unmodified polyolefins ill-suited for filter sheet applications in which a modified surface charge is desired for removing particles from an aqueous liquid. For example, many chemical charge modifiers (e.g., cationic resins, charged particles, etc.) adhere poorly, if at all, to conventional unmodified, hydrophobic polyolefin sheets.
In the past, chemical coatings and/or internal additives have been added to filter sheets made of inexpensive materials to impart desired properties. Many of these coatings and/or additives present problems related to cost, effectiveness, durability and/or the environment.
It has been proposed that biofunctional materials (e.g., proteins) can be deposited from solutions onto different substrates (i.e., sheets of materials) to modify the surface properties of the substrates and/or serve as a functionalized surface that can be chemically reactive. However, many of the economically desirable substrates (e.g., substrates formed of polymers such as polyolefins) have surfaces that are unsuitable for the rapid and inexpensive deposition of biofunctional materials, especially when durable, tightly bound coatings of satisfactory adherence are desired.
Even if inexpensive, durable, tenacious coatings could be adhered to an economically desirable substrate, coatings composed solely of biofunctional materials (e.g., proteins) may have limitations, especially if the coatings lacked the desired chemical characteristics such as, for example, modified surface charge characteristics.
Thus, there is still a need for a practical and inexpensive chemically charged modified filter for removing micron to sub-micron sized charged particles from an aqueous liquid. A need exists for such a filter formed from an unmodified, relatively inert, hydrophobic substrate such as, for example, an unmodified, relatively inert, polyolefin substrate. A need also exists for a method of removing charged, micron to sub-micron sized particles from aqueous liquids utilizing a practical and inexpensive chemically charge modified filter such as, for example, a chemically charge-modified filter formed from an unmodified, relatively inert, polyolefin substrate.
In addition to the needs described above, there is a need for a simple, practical and inexpensive chemically charge-modified filter for removing waterborne pathogens from aqueous liquid. This need also extends to a simple method for removing waterborne pathogens from aqueous liquids utilizing a practical and inexpensive chemically charge-modified filter.
One phenomenon observed with some filters having a modified surface charge characteristic is that the filters have different filtration efficiencies for different types of waterborne pathogens, such as, for example, different types of bacteria. That is, some filters having modified surface charges provide acceptable removal of some types of waterborne pathogens (e.g., some types of bacteria), but not others. The nature of this affinity appears to be difficult to predict. Since even relatively small differences in waterborne pathogen removal efficiency can be important, the discovery that a filter or filter system has an unpredictably strong affinity for a waterborne pathogen would be both unexpected and highly desirable, especially if the filter can be used to produce potable water. Meeting this need is important because removing waterborne pathogens from aqueous liquids in a practical and inexpensive manner remains a challenge in many parts of the world.
The present invention addresses some of the difficulties and problems discussed above by providing a hydrophobic polymer fiber having a cationically charged coating thereon, in which the coating includes a functionalized cationic polymer which has been crosslinked by heat. By way of example, the functionalized cationic polymer may be an epichlorohydrin-functionalized polyamine. As another example, the functionalized cationic polymer may be an epichlorohydrin-functionalized polyamido-amine.
The present invention also provides a fibrous filter which includes hydrophobic polymer fibers having a cationically charged coating thereon. The coating includes a functionalized cationic polymer which has been crosslinked by heat. As before, the functionalized cationic polymer is an epichlorohydrin-functionalized polyamine or an epichlorohydrin-functionalized polyamido-amine.
The present invention further provides a method of preparing a fibrous filter. The method involves providing a fibrous filter comprised of hydrophobic polymer fibers; treating the fibrous filter with an aqueous solution of a functionalized cationic polymer crosslinkable by heat under conditions sufficient to substantially coat the fibers with the functionalized cationic polymer, wherein the solution comprises the functionalized cationic polymer, a poly(vinyl alcohol), a polar solvent for the poly(vinyl alcohol), and water; and treating the resulting coated fibrous filter with heat at a temperature and for a time sufficient to crosslink the functionalized cationic polymer present on the hydrophobic polymer fibers. By way of example, the functionalized cationic polymer may be an epichlorohydrin-functionalized polyamine or an epichlorohydrin-functionalized polyamido-amine. Without wishing to be bound by theory, it is believed that the poly(vinyl alcohol) alters the normally hydrophobic surfaces of the fibers to an extent sufficient to promote the coating of the fibers by the functionalized cationic polymer. In addition, it is believed that some of the hydroxy groups present in the poly(vinyl alcohol) can crosslink with reactive groups present in the functionalized cationic polymer (such as epoxy groups) to form a durable, positively charged coating on the fibers.
The present invention additionally provides a method of preparing a fibrous filter. The method includes providing a fibrous filter comprised of hydrophobic polymer fibers; passing a solution of a functionalized cationic polymer crosslinkable by heat through the fibrous filter under conditions sufficient to substantially coat the fibers with the functionalized cationic polymer, wherein the solution includes the functionalized cationic polymer, a poly(vinyl alcohol), and water; and treating the resulting coated fibrous filter with heat at a temperature and for a time sufficient to crosslink the functionalized cationic polymer present on the hydrophobic polymer fibers. Again, the functionalized cationic polymer may be an epichlorohydrin-functionalized polyamine or an epichlorohydrin-functionalized polyamido-amine.
The term xe2x80x9chydrophobic polymerxe2x80x9d is used herein to mean any polymer resistant to wetting, or not readily wet, by water, i.e., having a lack of affinity for water. A hydrophobic polymer typically will have a surface free energy of about 40 dynes/cm (10xe2x88x925 newtons/cm or N/cm) or less. Examples of hydrophobic polymers include, by way of illustration only, polyolefins, such as poylethylene, poly(isobutene), poly(isoprene), poly(4-methyl-1-pentene), polypropylene, ethylene-propylene copolymers, and ethylene-propylene-hexadiene copolymers; ethylene-vinyl acetate copolymers; styrene polymers, such as poly(styrene), poly(2-methylstyrene), styrene-acrylonitrile copolymers having less than about 20 mole-percent acrylonitrile, and styrene-2,2,3,3,-tetrafluoro-propyl methacrylate copolymers; halogenated hydrocarbon polymers, such as poly(chlorotrifluoroethylene), chlorotrifluoroethylene-tetrafluoroethylene copolymers, poly(hexafluoropropylene), poly(tetrafluoroethylene), tetrafluoroethylene-ethylene copolymers, poly(trifluoroethylene), poly(vinyl fluoride), and poly(vinylidene fluoride); vinyl polymers, such as poly(vinyl butyrate), poly(vinyl decanoate), poly(vinyl dodecanoate), poly(vinyl hexadecanoate), poly(vinyl hexanoate), poly(vinyl propionate), poly(vinyl octanoate), poly(heptafluoroisopropoxyethylene), 1-heptafluoroisopropoxy-methylethylene-maleic acid copolymers, poly(heptafluoroisopropoxypropylene), poly-(methacrylonitrile), poly(vinyl alcohol), poly(vinyl butyral), poly(ethoxyethylene), poly(methoxy-ethylene), and poly(vinyl formal); acrylic polymers, such as poly(n-butyl acetate), poly(ethyl acrylate), poly[(1-chlorodifluoromethyl)tetrafluoroethyl acrylate], poly[di(chloro-fluoromethyl)fluoromethyl acrylate], poly(1,1-dihydroheptafluorobutyl acrylate), poly(1,1-dihydropentafluoroisopropyl acrylate), poly(1,1-dihydropentadeca-fluorooctyl acrylate), poly(heptafluoroisopropyl acrylate), poly[5-(heptafluoroiospropoxy)-pentyl acrylate], poly[11-(heptafluoroiospropoxy)undecyl acrylate], poly[2-(heptafluoropropoxy)ethyl acrylate], and poly(nonafluoroisobutyl acrylate); methacrylic polymers, such as poly(benzyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl meth-acrylate), poly(t-butyl methacrylate), poly(t-butylaminoethyl methacrylate), poly(dodecyl methacrylate), poly(ethyl methacrylate), poly(2-ethylhexyl methacrylate), poly(n-hexyl methacrylate), poly(dimethylaminoethyl methacrylate), poly(hydroxyethyl methacrylate), poly(phenyl methacrylate), poly(n-propyl methacrylate), poly(octadecyl methacrylate), poly(1,1-dihydropentadecafluorooctyl methacrylate), poly(heptafluoroisopropyl methacrylate), poly(heptadecafluorooctyl methacrylate), poly(1-hydrotetrafluoroethyl methacrylate), poly(1,1-dihydrotetrafluoropropyl methacrylate), poly(1-hydrohexafluoroisopropyl methacrylate), and poly(t-nonafluorobutyl methacrylate); polyethers, such as poly(chloral), poly(oxybutene)diol, poly(oxyisobutene)diol, poly(oxydecamethylene), poly(oxyethylene)-dimethyl ether polymers having molecular weights below about 1,500, poly(oxyhexamethylene)diol, poly(oxypropylene)diol, poly(oxypropylene)-dimethyl ether, and poly(oxytetramethylene); polyether copolymers, such as poly(oxyethylene) -poly(oxypropylene)-poly(oxyethylene) block copolymers, oxyethylene-oxypropylene copolymers having greater than about 20 mole percent oxypropylene, oxytetramethylene-oxypropylene copolymers, and block copolymers having oxyethylene-oxypropylene copolymer blocks separated by a poly(oxydimethylsilylene) block; polyamides, such as poly[imino(1-oxodecamethylene)], poly[imino(1-oxododecamethylene)] or nylon 12, poly[imino(1-oxohexamethylene)] or nylon 6, poly[imino(1-oxotetramethylene)] or nylon 4, poly(iminoazelaoyliminononamethylene), poly(iminosebacoyliminodecamethylene), and poly(iminosuberoyliminooctamethylene); polyimines, such as poly[(benzoylimino)ethylene], poly[(butyrylimino)ethylene], poly[(dodecanoylimino)ethylene], (dodecanoylimino)ethylene-(acetyleimino)trimethylene copolymers, poly[(heptanoylimino)ethylene], poly[(hexanoylimino)ethylene], poly{[(3-methyl)butyrylimino]ethylene}, poly[(pentadecafluorooctadecanoylimino)ethylene], and poly[(pentanoylimino)ethylene]; polyurethanes, such as those prepared from methylenediphenyl diisocyanate and butanediol poly(oxytetramethylene)diol, hexamethylene diisocyanate and triethylene glycol, and 4-methyl-1,3-phenylene diisocyanate and tripropylene glycol; polysiloxanes, such as poly(oxydimethylsilylene) and poly(oxymethylphenylsilylene); and cellulosics, such as amylose, amylopectin, cellulose acetate butyrate, ethyl cellulose, hemicellulose, and nitrocellulose.
As used herein, the terms xe2x80x9ccationically chargedxe2x80x9d in reference to a coating on a hydrophobic polymer fiber and xe2x80x9ccationicxe2x80x9d in reference to the functionalized polymer mean the presence in the respective coating and polymer of a plurality of positively charged groups. Thus, the terms xe2x80x9ccationically chargedxe2x80x9d and xe2x80x9cpositively chargedxe2x80x9d are synonymous. Such positively charged groups typically will include a plurality of quaternary ammonium groups, but they are not necessarily limited thereto.
The term xe2x80x9cfunctionalizedxe2x80x9d is used herein to mean the presence in the cationic polymer of a plurality of functional groups, other than the cationic groups, which are capable of crosslinking when subjected to heat. Thus, the functional groups are thermally crosslinkable groups. Examples of such functional groups include epoxy, ethylenimino, and episulfido. These functional groups readily react with other groups typically present in the cationic polymer. The other groups typically have at least one reactive hydrogen atom and are exemplified by amino, hydroxy, and thiol groups. It may be noted that the reaction of a functional group with another group often generates still other groups which are capable of reacting with functional groups. For example, the reaction of an epoxy group with an amino group results in the formation of a xcex2-hydroxyamino group.
Thus, the term xe2x80x9cfunctionalized cationic polymerxe2x80x9d is meant to include any polymer which contains a plurality of positively charged groups and a plurality of other functional groups which are capable of being crosslinked by the application of heat. Particularly useful examples of such polymers are epichlorohydrin-functionalized polyamines, which polymers include epichlorohydrin-functionalized polyamido-amines. Both types of polymers are exemplified by the Kymene(copyright) resins which are available from Hercules Inc., Wilmington, Del. Other suitable materials include cationically modified starches, such as such as RediBond, from National Starch. Desirably, the functionalized cationic polymer will be an epichlorohydrin-functionalized polyamine or an epichlorohydrin-functionalized polyamido-amine.
As used herein, the term xe2x80x9cthermally crosslinkedxe2x80x9d means the coating of the functionalized cationic polymer has been heated at a temperature and for a time sufficient to crosslink the above-noted functional groups. Heating temperatures typically may vary from about 50xc2x0 C. to about 150xc2x0 C. Heating times in general are a function of temperature and the type of functional groups present in the cationic polymer. For example, heating times may vary from less than a minute to about 60 minutes or more.
As stated earlier, the present invention provides a hydrophobic polymer fiber having a cationically charged coating thereon, in which the coating includes a functionalized cationic polymer which has been crosslinked by heat. By way of example, the functionalized cationic polymer may be an epichlorohydrin-functionalized polyamine. As another example, the functionalized cationic polymer may be an epichlorohydrin-functionalized polyamido-amine.
The present invention also provides a fibrous filter which includes hydrophobic polymer fibers having a cationically charged coating thereon. The coating includes a functionalized cationic polymer which has been crosslinked by heat. As before, the functionalized cationic polymer is an epichlorohydrin-functionalized polyamine or an epichlorohydrin-functionalized polyamido-amine.
In general, the fibrous filter will contain at least about 50 percent by weight of hydrophobic polymer fibers, based on the weight of all fibers present in the filter. In some embodiments, essentially 100 percent of the fibers will be hydrophobic polymer fibers. When other fibers are present, however, they generally will be cellulosic fibers, glass fibers, or mixtures thereof.
Sources of cellulosic fibers include, by way of illustration only, woods, such as softwoods and hardwoods; straws and grasses, such as rice, esparto, wheat, rye, and sabai; canes and reeds, such as bagasse; bamboos; woody stalks, such as jute, flax, kenaf, and cannabis; bast, such as linen and ramie; leaves, such as abaca and sisal; and seeds, such as cotton and cotton linters. Softwoods and hardwoods are the more commonly used sources of cellulosic fibers; the fibers may be obtained by any of the commonly used pulping processes, such as mechanical, chemimechanical, semichemical, and chemical processes. Examples of softwoods include, by way of illustration only, longleaf pine, shortleaf pine, loblolly pine, slash pine, Southern pine, black spruce, white spruce, jack pine, balsam fir, douglas fir, western hemlock, redwood, and red cedar. Examples of hardwoods include, again by way of illustration only, aspen, birch, beech, oak, maple and gum.
The hydrophobic polymer fibers desirably will be fibers prepared from thermoplastic polyolefins, or mixtures thereof. Examples of thermoplastic polyolefins include polyethylene, polypropylene, poly(1-butene), poly(2-butene), poly(1-pentene), poly(2-pentene), poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), and the like. In addition, the term xe2x80x9cpolyolefinsxe2x80x9d is meant to include blends of two or more polyolefins and random and block copolymers prepared from two or more different unsaturated monomers. Because of their commercial importance, the most desirable polyolefins are polyethylene and polypropylene.
The fibrous filter (either before or after processing) may have a basis weight ranging from about 6 gsm to about 400 gsm. For example, the fibrous filter may have a basis weight ranging from about 12 gsm to about 250 gsm. Desirably, the fibrous filter may have a basis weight ranging from about 17 gsm to about 102 gsm. However, any number of the fibrous filters of the present invention may be joined together or joined to other materials to form a consolidated material that may have a basis weight within the range of 6 gsm to 400 gsm or even greater (e.g., greater than 400 gsm).
The present invention further provides a method of preparing a fibrous filter. The method involves providing a fibrous filter comprised of hydrophobic polymer fibers; treating the fibrous filter with an aqueous solution of a functionalized cationic polymer crosslinkable by heat under conditions sufficient to substantially coat the fibers with the functionalized cationic polymer, wherein the solution comprises the functionalized cationic polymer, a poly(vinyl alcohol), a polar solvent for the poly(vinyl alcohol), and water; and treating the resulting coated fibrous filter with heat at a temperature and for a time sufficient to crosslink the functionalized cationic polymer present on the hydrophobic polymer fibers. By way of example, the functionalized cationic polymer may be an epichlorohydrin-functionalized polyamine or an epichlorohydrin-functionalized polyamido-amine.
As a practical matter, the aqueous solution of the functionalized cationic polymer typically will include from about 0.1 to about 2 percent by weight of the functionalized cationic polymer, from about 0.1 to about 4 percent by weight of the poly(vinyl alcohol), and from about 10 to about 50 percent by weight of the polar solvent, with the remainder of the solution being water. By way of example, the aqueous solution of the functionalized cationic polymer may include from about 0.2 to about 1 percent by weight of the functionalized cationic polymer, from about 0.1 to about 2 percent by weight of the poly(vinyl alcohol), and from about 15 to about 45 percent by weight of isopropyl alcohol, with the remainder of the solution being water.
Poly(vinyl alcohol) is manufactured commercially by the hydrolysis of poly(vinyl acetate). The physical properties of poly(vinyl alcohol) largely are a function of the degree of hydrolysis and molecular weight. The poly(vinyl alcohol) useful in the present invention is that which generally is referred to as hot water-soluble poly(vinyl alcohol). Such material is highly hydrolyzed, having a degree of hydrolysis of at least about 98 percent. Desirably, the poly(vinyl alcohol) will have a degree of hydrolysis of 99 percent or greater. The molecular weight of the poly(vinyl alcohol) typically will be at least about 10,000, which corresponds approximately to a degree of polymerization of at least about 200. Desirably, the poly(vinyl alcohol) will have a molecular weight of from about 15,000 to about 20,000, which corresponds approximately to a degree of polymerization range of from about 325 to about 435.
In general, the polar solvent may be any organic solvent in which the poly(vinyl alcohol) is partially or completely soluble. Examples of polar solvents include, by way of illustration only, lower alcohols, such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, and t-butyl alcohol; ketones, such as acetone, methyl ethyl ketone, and diethyl ketone; dioxane; and N,N-dimethylformamide. Desirably, the polar solvent will be isopropyl alcohol.
Finally, the present invention additionally provides a method of preparing a fibrous filter, in which the method includes providing a fibrous filter composed of hydrophobic polymer fibers; passing a solution of a functionalized cationic polymer crosslinkable by heat through the fibrous filter under conditions sufficient to substantially coat the fibers with the functionalized cationic polymer, wherein the solution includes the functionalized cationic polymer, a poly(vinyl alcohol), and water; and treating the resulting coated fibrous filter with heat at a temperature and for a time sufficient to crosslink the functionalized cationic polymer present on the hydrophobic polymer fibers. Again, the functionalized cationic polymer may be an epichlorohydrin-functionalized polyamine or an epichlorohydrin-functionalized polyamido-amine.
Depending upon the functionalized cationic polymer, it may be either desirable or necessary to adjust the pH of the aqueous solution containing the polymer. For example, aqueous solutions of epichlorohydrin-functionalized polyamines or epichlorohydrin-functionalized polyamido-amines desirably have pH values which are basic or slightly acidic. For example, the pH of such solutions may be in a range of from about 6 to about 10. The pH is readily adjusted by means which are well known to those having ordinary skill in the art. For example, the pH may be adjusted by the addition to the polymer solution of typically dilute solutions of a mineral acid, such as hydrochloric acid or sulfuric acid, or an alkaline solution, such as a solution of sodium hydroxide, potassium hydroxide, or ammonium hydroxide.
The solution of the functionalized cationic polymer may be passed through the fibrous filter by any means known to those having ordinary skill in the art. For example, the solution may be xe2x80x9cpulledxe2x80x9d through the filter by reducing the pressure on the side of the filter which is opposite the side against which the solution has been applied. Alternatively, the solution may be forced through the filter by the application of pressure.
Once the fibers of the filter have been coated with the functionalized cationic polymer, the polymer is crosslinked by the application of heat at a temperature and for a time sufficient to crosslink the functional groups present in the polymer. Temperatures typically may vary from about 50xc2x0 C. to about 150xc2x0 C. Heating times in general are a function of temperature and the type of functional groups present in the cationic polymer. For example, heating times may vary from about 1 to about 60 minutes or more.
The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or the scope of the present invention. In the examples, all parts and percents are by weight.